Ternary aluminum-copper-cadmium alloy



United States Patent US. Cl. 75-134 3 Claims ABSTRACT OF THE DISCLOSUREA tertiary alloy consisting of aluminum, cadmium and copper in specifiedproportions is used as a starting material in the preparation ofRaney-type ternary alloy catalyst useful in selective hydrogenation ofnap-unsaturated carbonyl compounds, unsaturated fatty acids and unsatu'rated fatty acid esters.

This application is a division of copending application, Ser. No.466,435, filed June 23, 1965, now Pat. No. 3,412,042 which is acontinuation-in-part of copending application Ser. No. 340,485, filedIan. 27, 1964 (now abandoned), which is in turn a continuation-in-partof application Ser. No. 223,249, filed Sept. 12, 1962 and now abandoned.

The present invention embodies two aspects, both involving to newcatalysts, their production, and their use.

In the first aspect, the catalyst is a Raney copper cadmium catalystprepared from a ternary alloy of about 30 to 60 percent by weight ofaluminum and the remainder copper and cadmium. The cadmium content isabout 4 to percent by weight of said remainder, and the copper contentis about 96 to 85 percent by Weight of said remainder.

In the second aspect, the catalyst is a Raney copper cadmium catalystprepared from a ternaryalloy of about to 60 percent by weight ofaluminum, the remainder being copper and cadmium. The cadmium content isabout 1 to slightly less than 4 percent by weight of said remainder, andthe copper content is from a little more than 96 to about 99 percent byweight of said remainder.

Said catalysts are used in the production of a,,8-unsaturated alcoholsby hydrogenating c p-unsaturated aldehydes and by hydrogenatinga,,8-unsaturated ketones. Said catalysts are also useful in theproduction of unsaturated higher aliphatic alcohols by hydrogenatingeither unsaturated fatty acids or unsaturated fatty acid esters.

In hydrogenating a,B-unsaturated aldehydes and ketones using an ordinaryhydrogenation catalyst, it is very difficult to produce thecorresponding unsaturated alcohol in a satisfactory yield, since thedouble bond in the unsaturated aldehyde or ketone is more easilyhydrogenated than the carbonyl group.

The present catalysts are hydrogenation catalysts which have a highdegree of specificity and which permit the production of0a,}8-11I1S3t1113t6d alcohols from a,,8-unsaturated carbonyl compoundsthrough selective hydrogenation with a high yield.

Thus, an object of the invention is to provide novel activehydrogenation catalysts to be used for the production of cap-unsaturatedalcohols by selective hydrogenation of u,,8-unsaturated carbonylcompounds. Another object of the invention is to provide a method forpreparing such catalysts to be used for the production ofa,;8unsaturated alcohols by selective hydrogenation of a,,8-unsaturatedcarbonyl compounds.

Other objects are apparent from the following description.

The invention, in the first aspect, provides a method for preparing acatalyst used for the production of 11,5- unsaturated alcohols byhydrogenation of a,B-unsaturated carbonyl compounds in gaseous phase,which comprises melting a mixture of aluminum, copper and cadmiumcontaining 30 to 60% by weight of aluminum, and the remainder of copperand cadmium, the proportion of cadmium in the remainder being 4 to 15%by weight, to form a molten ternary alloy, rapidly cooling and thenpulverizing said alloy, treating said pulverized alloy with an aqueousalkali solution, washing said alloy with water and removing theresultant Raney copper cadmium catalyst composition. A catalystcomposition is obtained which is efifective in the hydrogenation processof this invention. It is highly selective and will accomplish theobjects of the invention.

The resultant catalyst composition is a Raney copper cadmium catalystwhich possesses a high degree of selectivity. It is composed essentiallyof 1 to 50 percent by weight of aluminum and a remainder :of cadmium andcopper with cadmium being 4 to 15 percent by weight of this remainder.The surface area of the catalysts ranges from 5 to 70 square meters pergram (m. /g.). The composition which is preferred is that which isprepared from ternary alloy containing 40 to 50 percent by weight (wt.percent) :of aluminum, 3 to 7 wt. percent cadmium and 43 to 57 wt.percent copper.

The invention, in the second aspect, provides a method for preparing acatalyst useful for producing o,fl-U1'1sattl rated alcohols byhydrogenating a,fi-unsaturated aldehydes and/or ketones. Said catalystis also useful in the production of unsaturated higher aliphaticalcohols by hydrogenating either unsaturated fatty acids or unsaturatedfatty acid esters.

The method described supra is also useful for the preparation of thesecond catalyst except that the starting mixture contains from 30 to 70%by weight of aluminum, the remainder being cadmium and copper. Thecadmium content is about 1 to less than 4% by weight of said remainderand the copper content is from a little more than 96 to about 99% byweight of said remainder. After melting this mixture, to form a moltenternary alloy, rapidly cooling and then pulverizing said alloy, treatingsaid pulverized alloy with an aqueous alkali solution, washing saidalloy with water, there is formed a Raney copper cadmium catalystcomposition containing 1 to 60 percent by weight of aluminum and aremainder of cadmium and copper, with cadmium being 1 to less than 4percent by weight of this remainder. The surface area of the catalystranges from 5 to 70 square meters per gram (m. /g.).

The Raney copper cadmium catalysts of the invention are prepared, forexample, as follows. Melting the alloy may be effected in a graphitecrucible using an electrofurnace. For easier preparation of the ternaryalloy of a definite composition, it is convenient preliminarily toprepare binary alloys of aluminum-copper and cadmiumcopper of definitecompositions, and then to fuse these mother alloys together to make theternary alloy. The molten alloy is well agitated with a silica rod,poured out from the graphite crucible onto a floor to form a plate 2 to3 mm. thick, cooled by water, and crushed to 2 to 3 mm. particles.

The alloy particles are treated with an aqueous alkali solution, such assodium or potassium hydroxide solution, washed with water, heated, andthen used for the hydrogenation. Upon the alkali-treatment, a greaterpart of the aluminum is dissolved out, as in the alkali treatment ofusual Raney-type catalyst.

EXAMPLE 1 Melt 176 g. (grams) of binary alloy block of aluminum-copper(40:48 by weight) in a No. 2 graphite crucible heated to about 700 C. byan electro-furnace. Add 24 g. of binary alloy block of cadmium-copper(1:1 by weight) thereinto under agitation. Agitate the resulting moltenalloy well with a silica rod and pour out onto a floor to make a plateof 2 to 3 mm. (millimeters) thickness. Cool said alloy rapidly withwater. After cooling, crush the alloy into 2 to 3 mm. particles.

Submerge fifty grams of the alloy in 1 kg. (kilogram) of aqueous 5%caustic soda solution at 100 to 101 C. for 2 hours, whereby a greaterpart of the aluminum in the alloy is dissolved out. After removal of thealkali solution, continually Wash the alloy with 3 liters of water undera hydrogen stream of 50 to 100 mm. Hg, and then fill a reaction tubewith the catalyst from the top under a hydrogen stream.

The following Table 1 shows the results of hydrogenation ofcrotonaldehyde by use of the resulting catalyst, and those by use ofcatalyst obtained by heat-treatment of the filled catalyst at 275 C.under a hydrogen stream for 3 hours.

thoroughly stirring the content. Discharge the resulting alloy on afloor while stirring with a silica rod. Immediately cool said resultingalloy rapidly with water and crush into a grain size of 200 to 250 mesh.The resulting alloy has a composition (wt. percent Cu:Cd:Al) of50.0:5.0:45.0. Submerge 10 g. of the thus obtained alloy grains in 1000g. of 10% aqueous caustic soda solution at 30 C. for minutes. Upon thealkali-treatment, most of the aluminum is dissolved out.

After the treatment, discard the alkali liquid and wash the thusobtained catalyst grains with water until the wash water is neutral. Theresulting catalyst has a composition (wt. percent Cu:Cd:Al) of88.0:8.6:3.2; and a surface area (m. g.) of 25.0. Fill a quartz tubewith the catalyst grains and heat said grains at 300 C. for 3 hours in ahydrogen current.

Add 3 g. of the above catalyst to 100 g. of methyl oleate (iodinenumber:89.1, saponification value:192.3, acid numberzO). Charge theresulting mixture in a shaking-type autoclave having an inner volume of1 1. (liter). Shake in the autoclave for 120 minutes at 260 C. under aninitial hydrogen pressure of 120 kg./cm. (kilograms per squarecentimeter) at 20 C., and cool. The reaction product has an iodinenumber of 72.8, an acid number of 54.1 and a hydroxyl value of 160.0.The hydroxyl value is the weight (mg) of caustic potassium required forneutralizing acetic acid formed by decom- TABLE 1 Catalyst Alloycomposition Composition Reaction Liquid space (wt. percent) (Wt.percent) Surface area pressure Reaction velocity Conversion Yield Cu:CdzAl Cu: CdzAl (n1. '-'/g.) Treatment (kg/cm. abs.) temp. C.) (l./l.hr.) (percent) (percent) 54. 0:6. 0:40. 0 72. 9:8. 1:19. 0 19. 0 275 C.,31118. 1 125 0, 66 2 0 g 3 under H2. 1 175 0.55 12. 6 80. 9 1 225 0. (i026. 8 79. 0 19. 3 Without 1 125 0. 60 35. 3 15. 0 heating. 1 175 0. 5848. 0 32. 3 1 225 0. 54 55. 0 5i). 8

EXAMPLE 2 posing the acetylated product obtained by acetylating 1 g.

Although the employment of the Raney copper cadmium catalyst preparedfrom varied composition of the alloy in each example obviates theinfluence of the proportion of catalyst metals in the alloy to activityand selectivity of the catalyst, Table 2 further clarifies the resultswhere the proportions of copper and cadmium are changed (at the constantamount of aluminum) in the alloy in the hydrogenation of crotonaldehydeto crotyl alcohol. Also, Table 2 reflects the use of a small proportionof aluminum in the catalyst.

of the sample.

EXAMPLE 4 A graphite crucible was heated at about a temperature of 700C. in an electric furnace. 194 g. of two component alloy mass consistingof aluminum and copper in a proportion of :47 by weight were melted inthis crucible. Then 6 g. of two component alloy mass consisting ofcadmium and copper in a proportion of 1:1 by weight was introducedtherein while stirring. While being stirred well by a bar of silica, thecontent was discharged on a TABLE 2 Catalyst Catalyst Alloy compositionComposition Reaction Liquid space (wt. percent) (Wt. percent) Surfacearea Heat pressure React1on velocity Conversion Yield CuzCdAl Cu; CdzAl(1n. /g.) Treatment (kg/cm. abs.) temp. C.) (l./l. hr.) (percent)(percent) 45.9141 50.0 :6.8:17.2 30.1 V 3 225 0.58 31.0 84.3 41911.7;504:2. 8:18. 3 30. 2 gfi g gl 3 225 0. 70 98.0 9.1 43.4:6.2:50.4.0:l0.3:l7.7 31.0 f 3 225 0.58 29.6 81,6 60.1:6.0:33.9 :7.1:21.8 8. 0 23 225 0.60 32.1 78.8

The present invention is further illustrated with reference to thefollowing examples, wherein the analytical values of each reactionproduct are measured on substance obtained by thoroughly saponifying theproduct after the removal of the catalyst, treating the saponifiedproduct with hydrochloric acid, washing the treated substance with waterand then topping the same under reduced pressure to remove methanol orbutanol completely.

EXAMPLE 3 In an electric furnace, heat a graphite crucible to about 700C. Melt 180 g. (grams) of an aluminum-copper 1:1 by weight ratio) binaryalloy lump in the crucible. Subsequently, charge 20 g. of acadmium-copper (1:1 by

floor, immediately cooled by water and after being cooled, crushed to200 to 250 mesh.

10 g. of the resulting alloy was treated with 1 kg. of 10 percentaqueous solution of sodium hydroxide at a temperature of 30 C. for 15minutes. After this treatment, the alkaline solution was discarded, andthe alloy was washed with water until washed solution becomes natural.The washed alloy was filled in a quartz tube and treated in a hydrogenatmosphere at a temperature of 290 C. for 3 hours.

5 g. of the above-mentioned catalyst was added to 100 g. of butyl oleate(iodine value 76.8, saponification value 168.2 and acid value 0.1). Thismixture was charged in an autoclave having an internal volume of 1 literand weight ratio) binary alloy lump in the crucible, while equipped witha stirrer and allowed to react at an initial hydrogen pressure of 130 lg./cm. (at 20 C.), at a temperature of 265 C. for 150 minutes. Theanalytical values of the product formed were as follows: iodine value70.3, acid value 49.8, hydroxyl value 157.0. The hydroxyl value wasexpressed as milligrams of potassium hydroxide required to neutralizeacetic acid produced by decomposing 1 gram of the acetylated product.

EXAMPLE 198.4 g. of a two component alloy mass consisting of aluminumand copper in a proportion of 34:15.6 by weight and 1.6 g. of a twocomponent alloy mass consisting of cadmium and copper in a proportion of1:1 were melted in a crucible by the method set forth in Example 4,while being stirred well, discharged on a floor, immediately cooled bywater and after being cooled, crushed into lumps of 3 to 5 millimeters.

50 g. of the crushed alloy was treated in 700 g. of percent sodiumhydroxide solution at a temperature ranging from 100 to 101 C. for 3hours and washed sufiiciently with water after discarding the alkalinesolution. The treated alloy was added to the middle of a reaction tubemade of SUS (trade name of a Japanese stainless steel manufacturer) andhaving an internal diameter of 18 mm. and length of 400 mm. andsubjected to heat treatment at a temperature of 275 C. for 3 hours undera hydrogen atmosphere. The so-obtained catalyst was used forhydrogenation of G-methyI-M-tetrahydrobenzaldehyde.

What is claimed is:

1. A ternary alloy comprising aluminum, cadmium and copper wherein theweight percent of aluminum is about to and the Weight percent of cadmiumis about 4 to 15% of the remainder, the essential balance being copper.

2. A ternary alloy comprising aluminum, cadmium and copper wherein theweight percent of aluminum is about 30 to 60% and the weight percent ofcadmium is about 1 to slightly less than 4% of the remainder, theessential balance being copper.

3. A ternary alloy comprising aluminum, cadmium and copper wherein theweight percent of aluminum is about 30 to and the weight percent ofcadmium is about 1 to slightly less than 4% of the remainder, theessential balance being copper.

References Cited' UNITED STATES PATENTS 3,355,282 11/1967 Kudo et a1.139 2,026,551 1/1936 Fink 75-439 1,658,757 2/1928 Bernhoeft 75139FOREIGN PATENTS 16,453 1903 Great Britain.

RICHARD O. DEAN, Primary Examiner US. Cl. X.R. 75139, 162

